Synthesis of pentafluorotellurium hypofluorite

ABSTRACT

The present invention concerns itself with a method for synthesizing hypofluorite compounds by utilizing fluorine fluorosulfate as a fluorinating agent and to a novel pentafluorotellurium hypofluorite compound prepared thereby.

STATEMENT OF GOVERNMENT INTEREST

The invention described herein may be manufactured and used by or for the Government for governmental purposes without the payment of any royalty thereon.

BACKGROUND OF THE INVENTION

This invention relates to hypofluorite compounds and to a novel method for their preparation. In a more particular aspect, this invention concerns itself with a novel route for effecting the synthesis of pentafluorotellurium hypofluorite (TeF₅ OF) using fluorine fluorosulfate as a reaction component.

Hypofluorite compounds are well known and find utility for a wide variety of industrial applications. They are particularly useful as fluorinating agents for introducing fluorine atoms into another compound, and as intermediates in synthetic reactions. At the present time, however, there is no simple and convenient process for producing these compounds. Until recently, the number of elements known to form hypofluorites was limited to the nonmetal main group elements of hydrogen, carbon, nitrogen, oxygen, sulfur, selenium, fluorine and chlorine.

Generally, the method used heretofore for the synthesis of these hypofluorites involved the fluorination of the corresponding hydroxyl compounds or their metal salts with elemental fluorine. An attempt was made by Seppelt et al, Inorg. Chem. 1973, 12, 2727, to apply this method to the synthesis of the hitherto unknown TeF₅ OF. The attempt was unsuccessful. An analogous method, however, proved fruitful in synthesizing TeF₅ OCl which led to the conclusion that TeF₅ OF is unstable or actually nonexistant. Additionally, further research efforts, as reported by Christe et al, Inorg. Chem., 1981, 20, 2104, proved to be successful in synthesizing a stable iodine hypofluorite with the observation that hypofluorites are generally more stable than the other hypohalites and the suggestion that TeF₅ OF should exist and should also be stable.

In line with the observations noted above, additional experimental efforts proved successful and a novel method for synthesizing TeF₅ OF was discovered. It was found that the hitherto unknown TeF₅ OF compound could be produced in stable form and in relatively high yield by a process which provided for the use of fluorine fluorosulfate as the fluorinating agent.

SUMMARY OF THE INVENTION

The present invention concerns itself with a novel method for synthesizing hypofluorites by utilizing fluorine fluorosulfate as a fluorinating agent. The method of this invention proved successful in synthesizing in high yield the novel compound, pentafluorotellurium hypofluorite. Synthesis is achieved by effecting a reaction between CsTeF₅ O and FOSO₂ F at relatively low temperatures.

Accordingly, the primary object of this invention is to provide a novel method for synthesizing hypofluorite compounds.

Another object of this invention is to provide a method for synthesizing hypofluorite compounds that utilizes fluorine fluorosulfate as a fluorinating agent.

Still another object of this invention is to provide a method for synthesizing the novel compound, pentafluorotellurium hypofluorite.

The above and still other objects and advantages of the present invention will become more readily apparent upon consideration of the following detailed description thereof.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Pursuant to the above-defined objects, the present invention is brought into effect by accomplishing a reaction between CsTeF₅ O and FOSO₂ F within a closed environment at temperatures ranging from about -10° to -45° C. The known methods for preparing hypofluorites are quite limited and attempts at using these previously known methods for producing the hitherto unknown TeF₅ OF have not been successful. For example, the fluorination of either CsTeF₅ O or KTeF₅ O with F₂ at -45° to -10° C. resulted only in the formation of TeF₆. However, with the present invention, it was found that a fairly high yield synthesis of TeF₅ OF could be accomplished by reacting CsTeF₅ O with FOSO₂ F at temperatures ranging from about -10° to -45° C. This reaction is illustrated by the following general equation:

    CsTeF.sub.5 O+FOSO.sub.2 F→CsSO.sub.3 F+TeF.sub.5 OF (1)

This novel reaction represents a new synthetic route to the preparation of hypofluorite compounds. Based on the general usefulness of the analogous ClOSO₂ F reagent for the syntheses of hypochlorites, it would appear that FOSO₂ F will become a similarly useful, versatile and general reagent for the synthesis of hypofluorite compounds.

When the synthesis of TeF₅ OF from CsTeF₅ O and FOSO₂ F was carried out above -45° C., the amount of TeF₆ by-product sharply increased. For example, at -10° C. and with a reaction time of 7 days, the TeF₆ to TeF₅ OF ratio in the product increased to 1:1. The use of an excess of CsTeF₅ O in this reaction was found advantageous for the product purification since it eliminated the need for separating TeF₅ OF from FOSO₂ F.

The reaction scheme for synthesizing the novel TeF₅ OF compound of this invention is further illustrated with greater specificity by Example I which follows.

EXAMPLE I

A 30 ml stainless steel Hoke cylinder was loaded with CsTeF₅ O (3.42 mmol) in the glove box. After evacuation and cooling of the cylinder to -196° C., FOSO₂ F (2.79 mmol) was added from the vacuum line. The closed cylinder was slowly warmed to -78° C. in a liquid nitrogen-CO₂ slush bath and finally kept at -45° C. for 9d. Upon recooling to -196° C. about 4-5 cm³ of noncondensable gas was observed to be present. This was pumped away and the condensable products were separated by fractional condensation in a series of U-traps cooled at -78°, -126°, and -196° C. The -78° C. fraction was TeF₅ OH (0.19 mmol) while the -196° C. fraction was TeF₆ (0.49 mmol).

A white solid was retained at -126° C. which changed to a colorless glass and melted, over a range of a few degrees, near -80° C. to a clear, colorless liquid. This material was identified as TeF₅ OF (1.91 mmol, 68% yield) based on its vapor density molecular weight; found, 256.2; calc., 257.6 g/mol. Further identification was based on its spectroscopic properties and on the preparation of derivatives. The observed weight loss of the solid (0.375 g) agreed well with that calculated (0.389 g) for the conversion of 2.79 mmol CsTeF₅ O to CsSO₃ F. Vapor pressure-temperature data of TeF₅ OF were measured: T°C., Pmm; -79.3, 16; -64.2, 45, -57.6, 63; -46.9, 108; -32.5, 210; -23.0, 312.

The TeF₅ OF compound of Example I is colorless as a gas and liquid. Its vapor pressure-temperature relationship for the range -79° to -23° C. is given by the equation

    log P.sub.mm =6.9022-1101.2/T°K.

The extrapolated boiling point is 0.6° C. The derived heat of vaporization is H_(vap) =5039 cal mol⁻¹ and the Trouton constant is 18.4 indicating little or no association in the liquid phase. Vapor density measurements showed that in the gas phase the compound is also not associated. A sharp melting point for TeF₅ OF was not observed because the samples showed a tendency to form a glass near -80° C. The compound appears to be completely stable at ambient temperature and has been stored in stainless steel cylinders for more than four months without any sign of decomposition.

The mass spectrum of TeF₅ OF is listed in Table I together with the spectra of TeF₅ OCl and TeF₅ OH which were measured for comparison. All of the listed fragments showed the characteristic tellurium isotope pattern and therefore the individual m/e listings were omitted for simplicity. The spectra of all three compounds show weak parent ions and TeF₃ ⁺ as the base peak.

                  TABLE I                                                          ______________________________________                                         MASS SPECTRUM OF TeF.sub.5 OF COMPARED TO THOSE                                OF TeF.sub.5 OCl AND TeF.sub.5 OH                                              TeF.sub.5 OF                                                                               TeF.sub.5 OCl TeF.sub.5 OH                                         assignt intens  assignt   intens                                                                               assignt intens                                 ______________________________________                                         TeF.sub.5 OF.sup.+                                                                     vw      TeF.sub.5 OCl.sup.+                                                                      vvw   TeF.sub.5 OH.sup.+                                                                     w                                      TeF.sub.4 OF.sup.+                                                                     vvw     TeF.sub.4 OCl.sup.+                                                                      vw    TeF.sub.4 OH.sup.+                                                                     vw                                     TeF.sub.5 O.sup.+                                                              TeF.sub.5.sup.+                                                                        s       TeF.sub.5.sup.+                                                                          s     TeF.sub.5.sup.+                                                                        vs                                     TeF.sub.4.sup.+                                                                        w       TeF.sub.4.sup.+                                                                          vw    TeF.sub.4.sup.+                                                                        w                                      TeF.sub.3 O.sup.+                                                                      m       TeF.sub.3 O.sup.+                                                                        ms    TeF.sub.3 O.sup.+                                                                      s                                      TeF.sub.3.sup.+                                                                        vs      TeF.sub.3 .sup.+                                                                         vs    TeF.sub.3.sup.+                                                                        vs                                     TeF.sub.2.sup.+                                                                        m       TeF.sub.2.sup.+                                                                          m     TeF.sub.2.sup.+                                                                        m                                      TeFO.sup.+                                                                             vw      TeFO.sup.+                                                                               w     TeFO.sup.+                                                                             w                                      TeF.sup.+                                                                              w       TeF.sup.+ w     TeF.sup.+                                                                              w                                      Te.sup.+                                                                               w       Te.sup.+  w     Te.sup.+                                                                               w                                      ______________________________________                                    

The infrared spectra of gaseous and of neon matrix isolated TeF₅ OF and the Raman spectra of liquid and solid TeF₅ OF were recorded and the observed frequencies are summarized in Table II.

                  TABLE II                                                         ______________________________________                                         VIBRATIONAL SPECTRA OF TeF.sub.5 OF                                            obsd freq, cm.sup.-1, and rel intens.sup.a                                                   Raman                                                            IR              liquid    solid                                                gas    Ne matrix    -55° C.                                                                           -110° C.                                                                       assignment.sup.b                          ______________________________________                                         1800 vw                                  2ν.sub.12                          1449 vw                                  2ν.sub.1                           1403 w                                   ν.sub.2 + ν.sub.8                908 vw                   905(0.4)p                                                                              904(0.8)                                                                              ν.sub.12                                        738.sup.c vs 738 sh dp                                                                              735 sh ν.sub.8                             738                                                                                        727 vs       721(1.1)p                                                                              721(1.3)                                                                              ν.sub.1                                         718 vw                                                                                                     impurity?                                          709 vw                                                                         668 vw       669(10)p                                                                               670(10)                                                                               ν.sub.2                                                      660(0.3)dp                                                                             662 sh ν.sub.5                             616 m       618 m        613(3.8)p                                                                              613(4) ν.sub.3                                         327 vs       325 sh, dp                                                                             325 sh ν.sub.9                             324 vs                                                                                     318 vs               319 sh ν.sub.10                                        308 vw       309(1.0)dp                                                                             309(1.6)                                                                              ν.sub.7                             300 sh      302 m        301(0.5)p                                                                              301 sh ν.sub.4                             280 mw      278 m        279(0.2)dp                                                                             279(0.2)                                                                              ν.sub.11                            241 mw      239 mw       240(0.2)p                                                                              240(0.2)                                                                              ν.sub.13                                                     166(0.1)dp                                                                             167(0.1)                                                                              ν.sub.14                           ______________________________________                                          .sup.a Uncorrected Raman intensities (peak heights)                            .sup.b For mode description see Table IV.                                      .sup.c Band shows tellurium isotope fine structure with splittings of          about 1.30 cm.sup.-1                                                     

The vibrational spectra of TeF₅ OF can be readily assigned as shown in Table III assuming a model with C_(4v) symmetry for the TeF₅ O part and C_(s) symmetry for the TeOF part of the molecule. ##STR1## Except for the symmetric out of phase, out of plane TeF₄ deformation mode in species B₁ which is usually observed for pseudo-octahedral molecules and is inactive under O_(h) symmetry, all fundamentals expected for the above C_(-4v) -C_(s) model were observed. Using the well established assignments of TeF₅ Cl, the assignments (see Table III) are straight forward and show for the two molecules almost identical frequencies for the TeF₅ part of the molecules. The weak band observed at about 906 cm⁻¹ in both the infrared and Raman spectra is characteristic for the OF stretching vibrations in hypofluorites.

                  TABLE III                                                        ______________________________________                                         Vibrational Spectra of TeF.sub.5 OF and their                                  Assignment Compared to Those of TeF.sub.5 Cl                                                obsd freq, cm.sup.-1, and rel intens.sup.a                                     TeF.sub.5 Cl                                                                              TeF.sub.5 OF                                           assign-                                                                               approx descrip-      RA    IR (gas,                                                                              RA                                    ment   tion of mode                                                                               IR (gas) (liquid)                                                                             matrix)                                                                               (liquid)                              ______________________________________                                         C.sub.4v                                                                       A.sub.1                                                                             ν.sub.1                                                                           νTeF     711 sh,m                                                                              708   727 vs 721                                                               (3.1)p       (1.1)p                                   ν.sub.2                                                                           ν.sub.s TeF.sub.4                                                                       662 vw 659          669                                                               (10)p        (10)p                                    ν.sub.3                                                                           νTeX     411 ms 413   616 m  613                                                               (7.7)p       (3.8)p                                   ν.sub.4                                                                           δ.sub.s TeF.sub.4                                                                    317 s  312   301 m  301                                                               (0.8)p       (0.5)p                              B.sub.1                                                                             ν.sub.5                                                                           ν.sub.s TeF.sub.4                                                                              651          660                                                               (0.8)dp      (0.3)dp                                  ν.sub.6                                                                           δTeF.sub.4                                                    B.sub.2                                                                             ν.sub.7                                                                           δ.sub. sciss TeF.sub.4                                                                      302   308 vw 309                                                               (0.5)dp      (1.0)dp                             E    ν.sub.8                                                                           ν.sub.as TeF.sub.4                                                                             726   738 vs 738 sh,                                                           (0.6)dp      dp                                       ν.sub.9                                                                           νFTeF.sub.4     327   327 vs 325 sh,                                                           (0.9)dp      dp                                       ν.sub.10                                                                          δXTeF.sub.4  167   318 vs (309-                                                             (1.8)dp      325)                                     ν.sub.11                                                                          δ.sub.as TeF.sub.4                                                                          259   280 mw 279                                                               (1.7)dp      (0.2)dp                             C.sub.s                                                                        A'   ν.sub.12                                                                          νXY                   908 vw 905                                                                            (0.4)p                              A"   ν.sub.13                                                                          δTeXY              240 mw 240                                                                            (0.2)p                                   ν.sub.14                                                                          τTeXY                       166                                                                            (0.1)dp                             ______________________________________                                          .sup.a Uncorrected Raman intensities (peak heights).                     

In preparing and testing the novel hypofluorite compound of this invention, the volatile materials were manipulated in a stainless steel vacuum line equipped with Teflon FEP (a polyperfluoroethylene propylene copolymer) U traps and 316 stainless steel bellows-seal valves and a Heise Bourdon tube-type pressure gauge. Telluric acid was prepared by the literature method of Mathers et al, Inorg. Syn., 1950, 3, 145, and also purchased from Cerac, Inc., and from Pfaltz and Bauer. Fluorosulfuric acid obtained from Allied was used both as received (light brown color) and after distillation to obtain the clear colorless material. The fluorine fluorosulfate was synthesized as described by Dudley et al, J. Am. Chem. Soc. 1956, 78, 290. The reaction of TeF₅ OH with either ClOSO₂ F or ClF was used to prepare TeF₅ OCl. Cesium and potassium chloride were oven dried, then cooled and powdered in the dry N₂ atmosphere of a glove box.

Infrared spectra were recorded in the range 4000-200 cm⁻¹ on a Perkin-Elmer Model 283 spectrophotometer calibrated by comparison with standard gas calibration points, and the reported frequencies are believed to be accurate to ±2 cm⁻¹. The spectra of gases were obtained using either a Teflon cell of 5-cm path length equipped with AgCl windows or a 10-cm stainless steel cell equipped with polyethylene windows which were seasoned with ClF₃. The spectra of matrix isolated TeF₅ OF and TeF₅ OCl were obtained at 6K with an Air Products Model DE202S helium refrigerator equipped with CsI windows. Research grade Ne(Matheson) was used as a matrix material in a mole ratio of 400:1.

The Raman spectra were recorded on a Cary Model 83 spectrophotometer using the 488 nm exciting line of an Ar-ion laser and a Claassen filter for the elimination of plasma lines. Quartz tubes (3 mm o.d.), closed by a metal valve, were used as sample containers in the transverse-viewing, transverse-excitation technique. A device described in Miller et al, Appl. Spectrosc. 1970, 24, 271 was used for recording the low-temperature spectra. Polarization measurements were carried out by method VIII as described by Claassen et al in J. Appl. Spectrosc. 1969, 23, 8.

From an examination of the above, it can be seen that the FOSO₂ F is a useful reagent for the synthesis of hypofluorites. Furthermore, it is shown that TeF₅ OF, as expected from comparison with TeF₅ OCl, TeF₅ OBr and FOIF₄ O, indeed exists and is a stable molecule. 

What is claimed is:
 1. The compound pentafluorotellurium hypofluorite.
 2. A method for synthesizing pentafluorotellurium hypofluorite which comprises the steps of:(a) effecting a reaction between (1) CsTeF₅ O and (2) FOSO₂ F at a temperature between about -45° to -10° C.; (b) continuing said hypofluorite reaction at said temperature for a period of time sufficient to prepare a pentafluorotellurium reaction product; and (c) separating said reaction product.
 3. A method in accordance with claim 2 wherein said temperature is about -45° C.
 4. A method in accordance with claim 2 wherein said period of time is about nine days. 